Electron-deficient viologens are widely used as ligands or structure-directing agents(SDAs)to synthesize crystalline X-ray induced photochromic materials.Here,a new rational strategy of anion-directed fold-ing a flexi...Electron-deficient viologens are widely used as ligands or structure-directing agents(SDAs)to synthesize crystalline X-ray induced photochromic materials.Here,a new rational strategy of anion-directed fold-ing a flexible cation(H_(2)imb)^(2+)((H_(2)imb)^(2+)=di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane)has been developed.Electron-donating Cl−and(ZnCl4)2−are used to direct folding a flexible electron-deficient(H_(2)imb)^(2+)cation.Three complexes(H_(2)imb)(NO_(3))2(1),(H_(2)imb)Cl2·H_(2)O(2),and(H_(2)imb)ZnCl4(3)have been synthesized in which(H_(2)imb)^(2+)crystallize in an anti-conformation,88.8°-gauche,and 51.8°-gauche,respectively.In contrary to X-ray silent complex 1,X-ray induced photochromism has been achieved in both complex 2 and 3.An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of(H_(2)imb)^(2+)has been validated to be critical to yield colored long-lived charge-separated states.展开更多
The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stab...The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stable under OER operating conditions,exhibits inherently poor OER activity from experimental observations.Herein,we doped a series of metal elements to regulate the ZrO_(2)catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions.Microkinetic modeling as a function of the OER activity descriptor(G_(O*)-G_(HO*))displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO_(2)surface,among which Fe and Rh(in the form of single-atom dopant)reach the volcano peak(i.e.the optimal activity of OER under the potential of interest),indicating excellent OER performance.Free energy diagram calculations,density of states,and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO_(2),leading to low OER overpotential,high conductivity,and good stability.Considering cost-effectiveness,single-atom Fe doped ZrO_(2)emerged as the most promising catalyst for OER.This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.展开更多
Magnesium(Mg)is a promising alternative to lithium(Li)as an anode material in solid-state batteries due to its abundance and high theoretical volumetric capacity.However,the sluggish Mg-ion conduction in the lattice o...Magnesium(Mg)is a promising alternative to lithium(Li)as an anode material in solid-state batteries due to its abundance and high theoretical volumetric capacity.However,the sluggish Mg-ion conduction in the lattice of solidstate electrolytes(SSEs)is one of the key challenges that hamper the development of Mg-ion solid-state batteries.Though various Mg-ion SSEs have been reported in recent years,key insights are hard to be derived from a single literature report.Besides,the structure-performance relationships of Mg-ion SSEs need to be further unraveled to provide a more precise design guideline for SSEs.In this viewpoint article,we analyze the structural characteristics of the Mg-based SSEs with high ionic conductivity reported in the last four decades based upon data mining-we provide big-data-derived insights into the challenges and opportunities in developing next-generation Mg-ion SSEs.展开更多
基金supported by National Natural Science Foundation of China(No.92261109)Natural Science Foundation of Fujian Province(No.2020J05080)+3 种基金Project Funded by China Postdoctoral Science Foundation(No.2023M733496)Natural Science Foundation of Xiamen(No.3502Z20206080)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR110)Recruitment Program of Global Youth Experts,Youth Innovation Promotion Association CAS(No.2021302).
文摘Electron-deficient viologens are widely used as ligands or structure-directing agents(SDAs)to synthesize crystalline X-ray induced photochromic materials.Here,a new rational strategy of anion-directed fold-ing a flexible cation(H_(2)imb)^(2+)((H_(2)imb)^(2+)=di-protonated 2,3-bis(imidazolin-2-yl)-2,3-dimethylbutane)has been developed.Electron-donating Cl−and(ZnCl4)2−are used to direct folding a flexible electron-deficient(H_(2)imb)^(2+)cation.Three complexes(H_(2)imb)(NO_(3))2(1),(H_(2)imb)Cl2·H_(2)O(2),and(H_(2)imb)ZnCl4(3)have been synthesized in which(H_(2)imb)^(2+)crystallize in an anti-conformation,88.8°-gauche,and 51.8°-gauche,respectively.In contrary to X-ray silent complex 1,X-ray induced photochromism has been achieved in both complex 2 and 3.An intermolecular charge-transfer mechanism has been elucidated and the anion directed folding of(H_(2)imb)^(2+)has been validated to be critical to yield colored long-lived charge-separated states.
基金the funding support from the Research Grants Council of the Hong Kong Special Administrative Region,China[Project No.CityU11308923]the Basic Research Project from Shenzhen Science and Technology Innovation Committee in Shenzhen,China(No.JCYJ20210324134012034)+5 种基金the Applied Research Grant of City University of Hong Kong(project No.of 9667247)Chow Sang Sang Group Research Fund of City University of Hong Kong(project No.9229123)the funding supported by the Seed Collaborative Research Fund Scheme of State Key Laboratory of Marine Pollution which receives regular research funding from Innovation and Technology Commission(ITC)of the Hong Kong SAR Governmentthe JSPS KAKENHI(No.JP23K13703 and JP23KF0102)the high-level science and technology talents project of Lvliang City(No.2022RC07)foundation of Shanxi supercomputing center of China(No.11sxsc202301).
文摘The design of cost-effective electrocatalysts is an open challenging for oxygen evolution reaction(OER)due to the“stable-oractive”dilemma.Zirconium dioxide(ZrO_(2)),a versatile and low-cost material that can be stable under OER operating conditions,exhibits inherently poor OER activity from experimental observations.Herein,we doped a series of metal elements to regulate the ZrO_(2)catalytic activity in OER via spin-polarized density functional theory calculations with van der Waals interactions.Microkinetic modeling as a function of the OER activity descriptor(G_(O*)-G_(HO*))displays that 16 metal dopants enable to enhance OER activities over a thermodynamically stable ZrO_(2)surface,among which Fe and Rh(in the form of single-atom dopant)reach the volcano peak(i.e.the optimal activity of OER under the potential of interest),indicating excellent OER performance.Free energy diagram calculations,density of states,and ab initio molecular dynamics simulations further showed that Fe and Rh are the effective dopants for ZrO_(2),leading to low OER overpotential,high conductivity,and good stability.Considering cost-effectiveness,single-atom Fe doped ZrO_(2)emerged as the most promising catalyst for OER.This finding offers a valuable perspective and reference for experimental researchers to design cost-effective catalysts for the industrial-scale OER production.
基金supported by the Ensemble Grant for Early Career Researchers 2022-2023 and the 2023 Ensemble Continuation Grant of Tohoku University,the Hirose Foundation,and the AIMR Fusion Research Grantsupported by JSPS KAKENHI Nos.JP23K13599,JP23K13703,JP22H01803,JP18H05513,and JP23K13542.F.Y.and Q.W.acknowledge the China Scholarship Council(CSC)to support their studies in Japan.
文摘Magnesium(Mg)is a promising alternative to lithium(Li)as an anode material in solid-state batteries due to its abundance and high theoretical volumetric capacity.However,the sluggish Mg-ion conduction in the lattice of solidstate electrolytes(SSEs)is one of the key challenges that hamper the development of Mg-ion solid-state batteries.Though various Mg-ion SSEs have been reported in recent years,key insights are hard to be derived from a single literature report.Besides,the structure-performance relationships of Mg-ion SSEs need to be further unraveled to provide a more precise design guideline for SSEs.In this viewpoint article,we analyze the structural characteristics of the Mg-based SSEs with high ionic conductivity reported in the last four decades based upon data mining-we provide big-data-derived insights into the challenges and opportunities in developing next-generation Mg-ion SSEs.
